CN101006012B - Powdered lithium transition metal oxide having doped interface layer and outer layer and method for preparation of the same - Google Patents

Powdered lithium transition metal oxide having doped interface layer and outer layer and method for preparation of the same Download PDF

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CN101006012B
CN101006012B CN2005800279273A CN200580027927A CN101006012B CN 101006012 B CN101006012 B CN 101006012B CN 2005800279273 A CN2005800279273 A CN 2005800279273A CN 200580027927 A CN200580027927 A CN 200580027927A CN 101006012 B CN101006012 B CN 101006012B
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metal oxide
lithium transition
transition metal
lithium
cation
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CN101006012A (en
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延斯·M·保尔森
裴畯成
张在业
金文珠
朴洪奎
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LG Energy Solution Ltd
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LG Chemical Co Ltd
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Abstract

The present invention provides a powdered lithium transition metal oxide useful as a major component for cathode active material of rechargeable lithium batteries, comprising a lithium transition metal oxide particle, a doped interface layer formed near the surface of the particle, and a thermodynamically and mechanically stable outer layer, and a method of preparing the same.

Description

Have doping type middle layer and outer field powdered lithium transition metal oxide and preparation method thereof
Technical field
The present invention relates to can be used as the powdered lithium transition metal oxide and preparation method thereof of main ingredient of the positive active material of chargeable lithium cell.More specifically, the invention provides powdered lithium transition metal oxide, it comprises lithium transition metal oxide particle, in cation doping type middle layer that the near surface of described particle forms with have thermodynamic stability and the skin of mechanical stability, described doping type middle layer is lithium transition-metal oxide and the reaction product that cationic strong lithium acceptor compound is provided.
Background technology
Wish to improve the energy density of lithium ion battery.This realizes by increasing operating voltage and/or increase capacity usually.For example, LiCoO 2Base battery is charged to about 4.2V and LiCoO under this voltage usually 2Capacity be lower than 150mAh/g.On the other hand, LiNiO 2Base battery is charged to lower voltage.
With respect to Li/Li +Increase LiCoO 2The charging voltage to 4.3 of base battery, 4.4 or 4.5V can significantly increase LiCoO 2Reversible capacity to about 155,175 or 195mAh/g.LiNiO 2Base battery more can reach similar capacity under the low voltage.Yet, increase charging voltage and cause some problems, as gas excessively emit, the excessive formation of cell resistance, ionogen decomposition etc.These problems especially at high temperature circulate or become more serious when storing.
A lot of open and patent documentation has proposed the coating method on the surface of protection positive electrode active materials (anodal active material), and has improved the high-voltage cyclical stability by this method and be proved.Yet, under many circumstances, observed improvement is from effective coating, but from clad material shorter air exposure time (Z.Chen after thermal treatment, J.R.Dahn, Electrochemical and solid state letters 7 (1) A11-A14).Commercial battery is applied above-mentioned clad material can not limit solution high-voltage and high temperature problem.
Can improve material character to a certain extent although confirmed to avoid for a long time air exposure, especially in room temperature circulation and compact battery, but in large-scale production, be difficult to usually shorten the air exposure time, more significantly do not improving related properties under exacting terms such as high-voltage and the high temperature.
In order to address these problems, several pieces of patent disclosures have proposed interpolation LiF; For example, U.S. Patent Publication 2004-91780 A1 disclosed before solid state reaction and to have added LiF and LiOH in blended oxyhydroxide, and U.S. Patent Publication 2002-14222 A1 discloses the doping halogen to high crystallization LiCoO 2In.Yet the film forming character of LiF is very poor usually, because LiF is not the lithium acceptor and do not contain foreign cation, therefore lacks chemical reaction between LiF and particle surface.Like this, the protection on surface is poor, thereby can not substantially improve high temperature/high-voltage character, perhaps need to add a large amount of LiF, yet this has reduced capacity.
As another kind of method, U.S. Patent Publication 2003-104279 A1 discloses to LiCoO 2The middle MgF that adds as doped compound 2MgF 2Can be applied to spinel or Li-Ni-Mn-Co sill, but at LiCoO 2Situation in do not recommend to use.At first, for LiCoO 2, Mg 2+Than Al 3+It or not the doping agent that is more suitable for.And by LiCo1-xAl xO 2The sosoloid of expression, that is, and LiCoO 2With the sosoloid of Al, be known, do not confirm that as yet whether sosoloid can be from LiCoO 2Obtain with Mg.If LiCoO 2Can exist with the solid solution of Mg, will obtain defective structure and depart from representative so the desirable Li that forms of attitude solution IM IIIO 2Secondly, MgF 2Fusing point very high, therefore, the reaction kinetics on the surface is very low and reduce to form the tendency of thin protective membrane.
United States Patent (USP) 6,613,479 disclose to stratiform LiMnO 2Middle doped with fluorine comprises adulterated LiMnO 2, wherein inhomogeneous material is through processing, and Mn is tervalent.Yet the material in the above-mentioned patent prepares under the low temperature rare gas element and has poor degree of crystallinity usually.As will be described, powdered lithium transition metal oxide of the present invention can prepare in air and be still stable and be crystallization in air, and in addition, manganese is quaternary.
In addition, many prior art document descriptions various coatings, equate as oxide compound, phosphoric acid salt, borate, glass, it is around the positive electrode active materials particle, and these coatings are usually by preparations such as paint-on technique such as dip coating, sol-gel method, the submicron particle method that contains slurry, dry method cladding processes.For example, at United States Patent (USP) 6,372, in 385, the positive powder last doping is advanced in the gel.Yet these prior art documents do not provide the lithium transition-metal oxide with high thermodynamic stability and mechanical stability.
Summary of the invention
Purpose of the present invention has solved the problems referred to above fully.
The purpose of this invention is to provide the powdered lithium transition metal oxide that has thermodynamic stability and mechanical stability and can be used for positive electrode active materials.
Another object of the present invention provides the method for preparing powdered lithium transition metal oxide with simple method.
Another object of the present invention provides the positive electrode active materials that comprises powdered lithium transition metal oxide.
To achieve these goals, the invention provides powdered lithium transition metal oxide, it comprises lithium transition metal oxide particle, in cation doping type middle layer that the near surface of described particle forms with have thermodynamic stability and the skin of mechanical stability, described cation doping type middle layer is (i) lithium transition-metal oxide and the reaction product that cationic strong lithium acceptor compound (ii) is provided.Preferably, positively charged ion is Al, and strong lithium acceptor compound is a cryolithionite.
As mentioned above, powdered lithium transition metal oxide of the present invention has the skin that covers particle surface, and this skin is fine and close form of film, and has the doping type middle layer as the middle layer, and this doping type middle layer forms between particle surface and skin.
Lithium transition-metal oxide has stratiform or spinel crystal structure and can be by while LixMO 2Expression, wherein M is the transition metal that is selected from manganese, cobalt and nickel, or their two or more combination, x is the scope of 0＜x＜1.M also can contain a spot of other positively charged ion known in the art in addition.If M mainly is manganese then stoichiometry x is about 1.5, and in this case, crystalline structure is a spinel.If crystalline structure is lamellated, then stoichiometry x is about 1.
The doping type middle layer is the reaction product of following two types component: a kind of component is a lithium transition-metal oxide, and another kind of component is the strong lithium acceptor compound (hereinafter being called " primary salt " sometimes) that contains foreign cation, and it will hereinafter be described in detail.Strong lithium acceptor in foreign cation and the primary salt be used for elements doped lithium transition metal oxide particle surface and simultaneously from some lithium ions of lithium transition metal oxide particle surface extraction to activate this surface, make reaction take place, thereby the surface is converted into the doping type middle layer and forms outer.
According to the experiment that the inventor carries out, find that most preferred doping agent is Al or Al/Mg, most preferably the lithium acceptor is phosphate radical anion and/or fluorine anion.The preferred concentration of fluorine anion is for being 0.5～5 atom % with respect to each transition-metal cation, and the preferred concentration of phosphate radical anion is for being 0.2～2 atom % with respect to each transition-metal cation.
Skin is the compound that comprises lithium and strong lithium acceptor, and the some of them lithium comes the lithium transition-metal oxide under the comfortable strong lithium receptor acting.
The present invention also provides the method for preparing above-mentioned powdery lithium metal oxide, comprises step:
(a) use as strong lithium acceptor and contain the surface of the salt coating of powdered lithium transition-metal oxide precursor of foreign cation; With
(b) precursor that will be coated with salt experiences the thermal treatment that temperature is not less than 700 ℃.
Therefore, method of the present invention comprises that interpolation contains foreign cation and anionic salt (described negatively charged ion is strong lithium acceptor) arrives powdery lithium metal oxide precursor, during heating treatment foreign cation forms the doping type middle layer by the sosoloid reaction with lithium transition-metal oxide, and the lithium of negatively charged ion and extraction forms the skin with high thermodynamic stability.Preferably, negatively charged ion is an aluminium, and primary salt is a cryolithionite.
In addition, the invention provides the positive electrode active materials that comprises above-mentioned powdery lithium metal oxide.
Description of drawings
Fig. 1 is the FESEM photo of the Kry08-900 that produces in embodiment 1 according to the inventive method;
Fig. 2 is the Com-LiCoO that produces in embodiment 1 according to the inventive method 2The FESEM photo;
Fig. 3 is expression Kry08-900 of the present invention and Com-LiCoO as a reference 2Under the C/10 speed before Coin-shape cell prolongs circulation and voltage graph afterwards, described Coin-shape cell is not exposed to assembling among the embodiment 2 under the damp atmosphere at positive electrode active materials;
Fig. 4 is expression Kry08-900 of the present invention and Mg-F-LiCoO as a reference 2Under the C/10 speed before Coin-shape cell prolongs circulation and voltage graph afterwards, described Coin-shape cell is exposed to assembling among the embodiment 3 under the damp atmosphere at positive electrode active materials;
Fig. 5 is expression Kry08-900 and Com-LiCoO 2The O that contains at embodiment 5 2The figure that oxygen enclosed pasture in the heat-processed of atmosphere is measured;
Fig. 6 is the figure of the cyclical stability of 118g-Kry in the prolongation circulation of embodiment 8 of expression root invention; With
Fig. 7 is the figure of the cyclical stability of expression reference sample in the prolongation circulation of embodiment 7.
Embodiment
Powdered lithium transition metal oxide of the present invention can be used as the main ingredient of secondary battery positive active material.More specifically, powdered lithium transition metal oxide is stable aspect the surface reduction that is exposed to for a long time before the battery assembling under the air, and for electrolytical reaction aspect be stable, particularly under charging state, emit and realized high stable circulation and and the formation that reduced resistive layer thereby reduced gas.This improvement realizes that in conjunction with the doping type middle layer described skin forms by outer on the surface of lithium transition-metal oxide.
Lithium transition-metal oxide is by for example Li-Mn-O base spinel or Li-M-O 2Basic unit's shape transition metal oxide forms.The transition metal M of lamellar phase mainly is made up of manganese, nickel or cobalt.M can additionally contain a spot of cation doping thing such as Mg, Al, Ti, Cu, Fe, Zn, Ta, Cr, B, Ga etc., is no more than 10 atom %.Also contain other doping agent known in the art of less amount in addition, be no more than 2 atom %.Particularly preferred lithium transition-metal oxide is the LiCoO with layered crystal structure 2, but form and also observe similar benefit mutually for other lamellar phase for spinel, for example have the mixed type Li-Mn-Ni-Co-oxide compound of layered crystal structure.
Foreign cation in the doping type middle layer (" cation doping thing ") is such as Al 3 +, Mg 2+Deng positively charged ion, it can replace the transition-metal cation in the lithium transition-metal oxide.In preferred version, foreign cation is an aluminum ion.
We do not understand the necessity that can form the foreign cation of sosoloid with lithium transition-metal oxide fully.Middle layer between salt and lithium transition-metal oxide has chemical stability and mechanical stability by inference, because foreign cation can be used as " linker " between elements doped lithium transition metal oxide surface and secondary salt.Can argue be if A and C by the identical adulterated words of doping agent X, the interface between solid AB and salt CD is more stable; That is, the surface is positioned at solid A 1-xX xB and solid C 1-yX yBetween the D, wherein X is as the bridge joint positively charged ion.
The outer surface film that forms, this surface film has mechanical stability and also have the high thermodynamic stability of 5V at least with respect to Li/Li+ under the sub-condition of positive pole.This stability surpasses the bound energy of lithium in the lithium transition-metal oxide.
Preparation in accordance with the present invention, the surface of lithium transition metal oxide particle at first apply with the salt (" primary salt ") that contains foreign cation and the strong lithium acceptor of conduct.Term among the present invention " coating " is meant the part coating and all applies and be intended to comprise such situation that promptly wherein primary salt contacts with the lithium transition metal oxide particle surface portion.
Primary salt can be the mixture of single salt face or two or more salt faces.The feature of contained at least a salt face is strong lithium acceptor compound in the primary salt, has enough strong to go the degree of lithiumation (delithiate) from the lithium transition-metal oxide precursor in thermal treatment subsequently.The further feature of primary salt is the positively charged ion that contains as doping agent.Cation doping thing and lithium transition-metal oxide and/or go the lithiumation precursor to form sosoloid.Preferably, primary salt, or at least a salt precursor that wherein contains has low melting point.For example, primary salt has and is lower than 800 ℃ low melting point.
The phase that it is feature that primary salt contains with the strong lithium acceptor that contains foreign cation.Thereby this strong lithium receptor property of primary salt also can be deviate from lithium by easy and lithium reaction from lithium transition-metal oxide negatively charged ion causes.This negatively charged ion comprises such as but not limited to F -, PO 4 3-Deng.It is the negatively charged ion of 0.1～5 atom % that primary salt comprises with respect to each transition-metal cation.Thereby foreign cation is meant the positively charged ion that can diffuse into lithium transition-metal oxide replacement transition metal ion and comprises such as but not limited to Al 3+, Ca 2+, Mg 2+, Ba 2+Deng.Therefore, primary salt includes but not limited to alkaline-earth metal fluoride, Li-alkaline-earth metal fluoride, aluminum phosphate, aluminum fluoride etc., or its two or more mixture.
Preferred primary salt is cryolithionite (Li 3AlF 6), it has low melting point and is commercially available.In the ideal scheme, primary salt contains the Li of at least 30 weight % 3AlF 6, more preferably contain the Li of at least 50 weight % 3AlF 6, with respect to every transition metal, the total amount of aluminium foreign cation is 0.1-2 atom %, more preferably 0.2-1.5 atom %.
The experiment of carrying out according to the inventor, by two generation lithium salts such as LiF and Li 3PO 4Form and skin that the described primary salt of the application of the invention obtains has the high thermodynamic stability with respect to Li/Li+, and does not decompose being lower than under the 5V, does not decompose being lower than under the 4.5V at least.On the other hand, primary salt such as the Co-SO4 of other the vitriol of accepting lithium or muriate such as Ni-Cl also contain foreign cation and deviate from lithium from lithium transition-metal oxide, form the skin that contains lithium; Yet, the skin that after primary salt and lithium transition-metal oxide precursors reaction, forms have with respect to the stability of the difference of Li/Li+ can, and decompose being lower than under the 4.5V.Therefore, vitriol and chloride salt type self is excluded from the primary salt kind of the present invention's definition.
In some versions, primary salt can with other lithium salts such as Li 2CO 3, LiOH uses together with the balance lithium,, completely or partially carries out the lithium of embedding again of lithium transition-metal oxide etc. after forming the surface that is, or with additional salt such as LiPO 3Use together, the expectation additional salt strengthens the lithium of primary salt and accepts active.The amount of additional salt is 1～60 weight % based on the total amount of primary salt.
Therefore because primary salt is commercially available as cryolithionite, be omitted about its preparation method herein.
Coating can be undertaken by the whole bag of tricks known in the art.For example, can add the primary salt of fine powder form, carefully grind then (dry method coating).Perhaps, wet coating also is possible.Typical wet coating comprises that preparation contains gel, solution or the slurry of primary salt, is immersed in the lithium transition-metal positive pole in the gel.If primary salt has the submicron particle that fully is separated into slurry form, then can certain method control pH, ionic strength etc. usually, still prevent the magnetism between the primary salt particle to be implemented in magnetism or the sticking power between preceding surface of lithium transition-metal oxide and the primary salt particle surface.The result is to apply primary salt on the surface of lithium transition-metal oxide smoothly.
After applying primary salt, the lithium transition-metal oxide precursor experience that applies salt is not less than 700 ℃ thermal treatment.Thermal treatment temp is preferably 700 ℃～1020 ℃.If temperature is too low, then can not finish surface reaction.On the other hand, if temperature is too high, then the cation doping thing can disperse to enter particle too apace, and then the character of secondary salt/lithium transition-metal particle interface can deterioration.
Surprisingly, although primary salt such as cryolithionite are decomposed to form skin, the surface coverage of being finished by final skin is mainly limited by the fusing point of primary salt.At Li 3AlF 6Situation in, under the temperature of reaction that is lower than as the LiF fusing point of outer layer component, can realize that surface of good covers, thereby positive pole is adequately protected in air exposure and the battery that assembling.
In thermal treatment, the surface reaction of primary salt and lithium transition-metal oxidation forms doping type middle layer and skin (hereinafter being called " secondary salt " sometimes).Reaction comprises from the borderline region of lithium transition-metal oxide precursor deviates from lithium and to wherein embedding doping agent.The decomposition of secondary salt is different with the decomposition of primary salt in the skin.Secondary salt forms thin surface film.
As following examples as can be known, the character of finding lithium transition-metal oxide can significantly be improved after the thermal treatment that contains a small amount of fully powdered lithium transition metal oxide precursor of dispersive primary salt.For example, at LiCoO 2Particle and cryolithionite and Li 2CO 3Mixture thermal treatment after, involve the surface reaction that foreign cation embeds and lithium is deviate from and taken place, and during surface reaction, formed the thin layer that covers described particle with the stable secondary salt with mechanical stability of thermokinetics.
When using Li 3AlF 6During as primary salt, lithium ion from lithium transition-metal oxide, deviate from and the LiF that formed form of film as secondary salt.Similarly, when using AlPO4 as primary salt, the Li of form of film is deviate from and formed to lithium ion from lithium transition-metal oxide 3PO 4As secondary salt.In above-mentioned two kinds of situations, Al 3+As foreign cation.In the solution of the present invention, LiPO 3The additive that can be used as primary salt.
Surprisingly,, then do not have lithium from lithium transition-metal oxide, to deviate from, and do not form thin stable secondary salt protective membrane if secondary salt does not contain strong lithium acceptor.In addition, if primary salt cation hotchpotch not, then related properties can not substantially improve.Therefore, can reach a conclusion, deviate from by the lithium on surface that embed to form the doping type middle layer and form outer by secondary salt with foreign cation be indispensable for the remarkable improvement that realizes high temperature properties.
The present invention also provides the positive electrode active materials that comprises above-mentioned powdered lithium transition metal oxide.This positive electrode active materials preferably is used in the chargeable lithium ion battery of equipment.Because various components of chargeable anode active material of lithium ion battery and preparation method thereof are being known in the art, be omitted for being described in herein of its.
Although do not further describe, it is believed that those skilled in the art can use aforesaid explanation and following exemplary embodiment, implement and utilize the present invention and put into practice method required for protection.Following embodiment understands preferred version of the present invention specifically, but it is construed as limiting the present invention never in any form.
Embodiment
Embodiment 1
LiCoO with commercially available 10-20 μ m potato-like particle 2Powder (hereinafter is called Com-LiCoO 2) carefully with cryolithionite Li as primary salt 3AlF 6With Li as additional salt 2CO 3(2: the mixture through low energy ball milling 1w/w) mixes.Every Co (LiCoO 2In) the total content of Al (in the primary salt) be 0.8 atom %.900 ℃ of thermal treatments 5 hours in air, then sample is slowly cooled off, grind and sieve.Sample is called " Kry08-900 ".
For relatively, by FESEM research Kry08-900 and Com-LiCoO 2, its FESEM photo is shown in respectively among Fig. 1 and Fig. 2.Com-LiCoO 2When having very smooth surface, the surface irregularity of Kry08-900 proves surface reaction has taken place.
Embodiment 2
In an embodiment the Kry08-900 of Huo Deing and the experience 900 ℃ of heat treated Com-LiCoO 2(" heat treated Com-LiCoO 2") be stored in the sealed vial in the dry room.Be not exposed at positive pole and prepare Coin-shape cell (having Li-metal negative pole) under the damp atmosphere.
Under the C/5 speed (C1=150mA/g) before the high-tension electrochemistry circulation of 50 ℃ of high temperature and 3～4.5V and obtain Kry08-900 and heat treated Com-LiCoO afterwards 2Voltage graph.Cycling condition: 50 ℃ of following 61 circulations, C/5 is to 4.5V in charging, and during major part circulation (56 times circulate) discharge rate be C/5 to 3.0V, the result is as shown in Figure 3.As can be seen from Figure 3, the positive electrode material of modification is that Kry08-900 has the stability of improving greatly, higher capacity keeps and repressed greatly impedance forms.
Embodiment 3
Kry08-900, at 900 ℃ of heat treated Com-LiCoO 2With commercially available conduct the LiCoO that contains Mg-F with reference to sample 2Be exposed under the damp atmosphere that contains the small amount of ethanol steam, above 4 days.Afterwards, use these samples to prepare Coin-shape cell (having Li-metal negative pole) respectively.
Fig. 4 shows that the Kry08-900 that is exposed under the air and Mg-F reference sample are before the electrochemistry circulation that prolongs and voltage pattern afterwards.Not shown Com-LiCoO 2Voltage pattern because this sample shows serious deterioration.Under the condition identical, circulate with embodiment 2.As shown in Figure 4, the positive electrode material of modification is that Kry08-900 has the stability of improving greatly, higher capacity keeps and repressed greatly impedance forms.
Embodiment 4
For quantitative solubility surface alkali, the water that repeats to add about 20ml decant also in the positive electrode material of 15g.Collecting total amount is the solution of 80ml, by the amount of record pH curve determination alkali during slowly adding 0.1M HCl.
For Li 2CO 3Usually have two stage curves, a stage curve (LiOH type) considerable part derives from the ion-exchange (LiCoO on surface 2+ H 2O → Li 1-xH xCoO 2+ xLiOH+bH 2O).
Obtain (i) before the air exposure and Kry08-900 afterwards, (ii) before air exposure and Com-LiCoO afterwards 2(iii) before air exposure and the curve of Mg-F-reference afterwards.The result sums up in following table 1.
Table 1
Figure G05827927320070225D000111
From above table 1 as can be known, sample Kry08-900 has the stability of antagonism variation in air.
Embodiment 5
The Com-LiCoO that under air, exposes 2Flow down slowly heating with the Kry08-900 that under air, exposes in the argon gas atmosphere that contains 10ppm oxygen.Measure the oxygen uptake that oxidation sample absorbs by solid-state enclosed pasture oxygen volumetry from air.The result as shown in Figure 5.
Referring to Fig. 5, in the heat treatment process under containing the atmosphere of oxygen, Com-LiCoO 2Adsorption of oxygen, and Kry08-900 sample performance inertia.Quantitative analysis shows that surface modification makes surface-stable, attacks thereby resist surperficial aerial reduction.The titrating Li that in embodiment 4, obtains 2CO 3The integral molar quantity and the molar weight of the oxygen of absorption approximately similar.
Can obtain the following fact from the experimental result of embodiment 2～5:
(1) Com-LiCoO 2Form Li 2CO 3, and its surface is reduced when being exposed to air following time.Li 2CO 3Formation and the surface that is reduced high temperature/high-voltage character of obtaining non-constant.
(2) through heat treated Com-LiCoO 2Do not contain Li 2CO 3, and its surface is not reduced.Yet high temperature/high-voltage character is slightly improved.
(3) Mg-F-reference and Kry08-900 do not form Li 2CO 3Yet under the situation of Mg-F-reference, observe high temperature/high-voltage character and have only slight improvement.
(4) the high surface stability of the Kry08-900 performance surperficial aerial reductive of antagonism, and antagonism is in battery assembling back and electrolytical reaction.
Embodiment 6
Repeat the process identical with embodiment 1 and prepare Kry08-900, difference is that thermal treatment carries out and the Al component is 0.5 atom % at 850 ℃.As the reference sample, use the LiF of the fluorine that contains 3 atom % to prepare the LiF-sample as primary salt.
The FESEM of these samples studies show that the surfaceness of Kry08-900 increases, and the LiF-sample has the Com-LiCoO of being similar to 2The surface of smooth surface.Therefore, confirmed that LiF is not suitable as primary salt separately in preparation method of the present invention.
Embodiment 7
Repeat the process identical with embodiment 1, difference is to use core-shell LiMO 2(M=Co 0.8(Mn 1/2Ni 1/2) 0.2) as precursor, and thermal treatment is carried out at 920 ℃.More specifically, the interior region of white potato shaped particle is by LiCoO 2Composition and external region thereof are by LiMO 2(M ≌ Co 0.6(Mn 1/2Ni 1/2) 0.4) form.The particle that obtains after thermal treatment is become " 118g-Kry ".In addition, prepared reference sample in the same manner, difference is not use primary salt.Then, use these specimen preparation Coin-shape cells and carry out electrochemical test.These results are shown in Fig. 6 and 7.
Fig. 6 and 7 shows that the cyclical stability of 118g-Kry under 50 ℃ of high temperature obviously improves (heavy body reservation, impedance still less form).
Embodiment 8
By adding primary salt and thermal treatment commercially available sample is carried out modification.These commercially available samples have composition Li{Lix[Co respectively 1/6(Mn 1/2Ni 1/2) 5/6] 1-xO 2(x ≌ O.05) and LiCo 1/3Mn 1/3Ni 1/3O 2
As primary salt, use Li 3AlF 6And Li 2CO 3Mass ratio be 3: 1 mixture.The sample that is coated with salt is heated to 850 ℃.During heating treatment, lithium is from LiMO 2Deviate from, thereby slightly reduced Li-M-O 2Li: the M ratio, particularly near the surface, reduced the amount of solvable alkali.The excessive positively charged ion blended that do not cause of lithium still less significantly increases, and does not destroy rate capability.After thermal treatment, the surface of lithium transition-metal oxide is by the protection of the film of secondary salt, and is mixed by aluminium in the surface.Improved high temperature/high-voltage character.
Embodiment 9
Use stoichiometry (Li: M=1: Li (Mn 1) 1/2Ni 1/2) 0.8Co 0.2O 2As precursor.By adding with respect to every Li 2CO 3The Li of 2,4,7 and 10 atom % of the transition metal of form, grind then and prepare the sample that the Li stoichiometry increases 900 ℃ of thermal treatments.By this method, prepared and consisted of Li[Li xM 1-x] O 2The stratiform lithium transition-metal oxide of enrichment Li, wherein x ≌ 1,2,3.5 and 5%.The detailed analysis of lattice parameter and lattice volume shows that unit cell volume shrinks.Although the stoichiometry sample has
Figure G05827927320070225D000141
Volume, volumetric shrinkage is that the unit cell volume that about 0.12%, 5% lithium excess sample has is for every approximately lithium interpolation per-cent
Figure G05827927320070225D000142
Studied (Mn from Li 1/2Ni 1/2) 0.8Co 0.2O 2In lithium deviate from, since 5% excess sample, add Li 3AlF 6, using every transition metal is the aluminium of 0.5,1 and 2.5 atom %, grinds then and 900 ℃ of thermal treatments.
The detailed analysis of lattice parameter and lattice volume shows that structure cell increases so that finally reach approximately
Figure G05827927320070225D000143
This increase is deviate to cause by the anodal lithium according to following chemical reaction:
x?Li 3AlF 6+{Li}[M]O 2-n?O 2→6x?LiF+{Li 1-4x}[MAl x]O 2-3x。
Carry out the rietveld definition and verified the result.
Present embodiment relates to the character of accepting Li of Li-sodium aluminum fluoride primary salt.
Therefore described the present invention, obviously can change the present invention in every way, this change does not break away from spirit of the present invention and protection domain, and these changes are conspicuous to those skilled in the art.

Claims (16)

1. powdered lithium transition metal oxide, it comprises lithium transition metal oxide particle, in cation doping type middle layer that the near surface of described particle forms with have thermodynamic stability and the skin of mechanical stability, described cation doping type middle layer is (i) lithium transition-metal oxide and the reaction product that cationic strong lithium acceptor compound (ii) is provided
Wherein said lithium transition-metal oxide has stratiform or spinel crystal structure and by general formula Li xMO 2Expression, wherein M is the transition metal that is selected from manganese, cobalt and nickel, or their two or more combination, condition is that M also can further contain a spot of cation doping thing, described a spot of cation doping thing is selected from Mg, Al, Ti, Cu, Fe, Zn, Ta, Cr, B and Ga, and x is the scope of 0＜x＜1
Described strong lithium acceptor is a fluorine anion.
2. powdered lithium transition metal oxide according to claim 1, wherein said lithium transition-metal oxide are the LiCoO with layered crystal structure 2Or has a mixed type Li-Mn-Ni-Co-oxide compound of layered crystal structure.
3. powdered lithium transition metal oxide according to claim 1, wherein said foreign cation is i) Al or ii) Al and Mg.
4. powdered lithium transition metal oxide according to claim 3, wherein said foreign cation is Al.
5. powdered lithium transition metal oxide according to claim 1, the concentration of wherein said fluorine anion is 0.5～5 atom % with respect to each transition-metal cation.
6. powdered lithium transition metal oxide according to claim 1, wherein said skin is a surface film, this surface film has mechanical stability and also have the high thermodynamic stability of 5V at least with respect to Li/Li+ under anodal condition.
7. powdered lithium transition metal oxide according to claim 1, wherein said strong lithium acceptor is cryolithionite Li 3AlF 6And positively charged ion is an aluminium, and wherein the concentration of fluorine is 0.5-5 atom % with respect to each metallic cation.
8. powdered lithium transition metal oxide according to claim 1, wherein said strong lithium acceptor have and are lower than 800 ℃ low melting point.
9. prepare the method for the described powdered lithium transition metal oxide of claim 1, comprise step:
(a) use contains the surface of the primary salt coating of powdered lithium transition-metal oxide precursor of foreign cation and the strong lithium acceptor of conduct; With
(b) the precursor experience temperature that will be coated with salt is 700 ℃～1020 ℃ thermal treatment.
10. method according to claim 9, wherein said primary salt are the mixtures of single salt face or two or more salt faces.
11. method according to claim 9, wherein foreign cation is to be selected from Al 3+, Ca 2+, Mg 2+And Ba 2+In one or more.
12. it is the foreign cation of 0.1～5 atom % that method according to claim 9, wherein said primary salt contain with respect to each transition-metal cation.
13. method according to claim 9, wherein said primary salt contains the Li of at least 30 weight % 3AlF 6, and with respect to every transition metal, the total amount of aluminium foreign cation is 0.1～2 atom %.
14. method according to claim 9, wherein said primary salt also contains other Li in 1～60 weight % scope based on the gross weight of the salt that comprises primary salt 2CO 3, LiPO 3And/or the lithium salts of LiOH.
15. method according to claim 9, wherein said primary salt is Li 3AlF 6And Li 2CO 3Mixture, Li wherein 3AlF 6Content be at least 30 weight %.
16. be used for the positive electrode active materials of rechargeable lithium ion batteries, comprise the described powdered lithium transition metal oxide of claim 1.
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